Polymer curing system, air-curable composition and method of preparing the composition

ABSTRACT

A mercaptan-containing compound and a particular curing package comprise a composition which is curable on exposure to an atmosphere containing oxygen.

This application is a division of application Ser. No. 954,037, filedOct. 23, 1978 now U.S. Pat. No. 4,224,200.

FIELD OF THE INVENTION

This invention relates to a polymer curing system, to an air-curablecomposition, and to a method of producing the air-curable composition.In one aspect, it relates to a cured composition. In another aspect, itrelates to articles of manufacture prepared from such curedcompositions.

BACKGROUND OF THE INVENTION

Mercaptan-containing polymers having at least two terminal (i.e.,reactive) mercaptan groups can be easily cured at room temperature toproduce elastomers having excellent properties, such as for example,resistance to weathering, oil, ozone, and water which makes thesesuitable for a variety of uses. Because such polymers are easily curedand are resistance to the elements they have been widely used assealants and adhesives, as well as in many other applications. Thesemercaptan-containing polymers, however, have generally had thedisadvantage that a "curing agent" had to be added to the polymers justprior to their use.

When a sealant composition comprising at least two components must bemixed just prior to use, such a sealant composition is normally called a"two-package" sealant system; whereas, a sealant composition that can bepremixed and stored without a substantial amount of curing for areasonable period of time and thus is sold "ready to use" is called a"one-package" sealant system. A one-package sealant composition must becapable of remaining relatively uncured in a container for an extendedperiod of time, for example about six months, and then begin to cureafter and only after being exposed to environmental conditions, such asair, water, or light.

Two-package systems are often used as standards against whichone-package systems are compared because two-package systems have beenin use for a long period of time (and are thus well established) andbecause they generally have better performance properties thanone-component systems. However, one-package systems are generallypreferred systems since they can be applied directly from a containerwithout any necessity of mixing at the time of application and thusavoid the potential problem of improper mixing of the components.Several attempts have been made to develop one-package systems thatcontain both the sealant base and the curing agent and which areactivated only when exposed to normal environmental conditions. Anexample of a one-package system is disclosed in U.S. Pat. No. 3,225,017,wherein a mercaptan-terminated polysulfide-based composition is cured byexposure to moisture. That system requires much moisture to cure and,therefore, is not useful in relatively arid climates.

Another one-package system is disclosed in U.S. Pat. No. 3,991,039,wherein a mercaptan-containing polysulfide polymer-based composition iscured by exposure to air or oxygen. In that patent, a curing packagecomprising a combination of a thiuram disulfide and an iron or manganesecomplex is disclosed. However, that curing package does not effectivelycure all types of mercaptan-containing polymers; and, in particular, itdoes not effectively cure certain mercaptan-containing polymers whichcontain mostly monosulfide linkages with minor amounts of disulfide andpolysulfide linkages (and which are disclosed in U.S. Pat. No. 3,817,936and in recently allowed application having Ser. No. 737,948) suchpolymers generally remaining tacky for long periods of time when theabovedescribed curing package is mixed with them.

A curing package has now been found which effectively cures evenmercaptan-containing polymers with mostly monosulfide linkages. Thecompositions become tack-free to polyethylene film within a relativelyshort period of time and have good resilience.

It is an object of this invention to produce air-curable compositionswhich can be used to prepare "one-package" sealants.

It is a further object of this invention to produce air-cured sealantcompositions which cure rapidly.

Statement of the Invention

According to the invention, a curing system suitable for curingcomprises (a) at least one Group IA, IB, IIA, IIB, IVA, VA, or VIA metalsubstituted dithiocarbamate and (b) at least one Group VIIB or VIIImetal compound of a carboxylic acid or at least one Group VIIB or VIIImetal compound of a beta-diketone. In one embodiment, the above-recitedcuring system is used to cure a particular polymer. And in anotherembodiment, an air-curable composition is provided.

The above-recited curing system is useful for curingmercaptan-containing compounds having at least one mercaptan group permolecule.

In this specification, the periodic chart which was used was found inthe Chemical Rubber Company (CRC) Handbook of Chemistry and Physics,49th Edition.

In this application, the term "cure" means that the composition beingdescribed has changed from a pourable, spreadable, or extrudable stateto a condition in which the composition is not pourable, spreadable, orextrudable. Generally, the cured composition has a surface that istack-free either to finger touch or to polyethylene film.

In this application, the term "mercaptan" should be understood to besynonymous with "thiol".

The compositions of the invention can be used as sealants and adhesivesto great advantage since they cure rapidly and effectively merely onexposure to air or oxygen, becoming tack-free to polyethylene filmwithin a relatively short period of time. They require no mixing ofingredients just prior to their use, and they can be stored with littleor no side effects long periods of time.

It is believed that oxygen is the active ingredient which operates toactivate the curing agent. Therefore, besides air, any otheroxygen-containing atmosphere will be expected to effect this activation.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In the practice of the invention, any material containing at least onemercaptan group will be expected to cure by the curing system describedbelow. This includes both monomers, as well as polymers. However,polymers are preferred as the base material (i.e., the material to becured) in the practice of the invention because of economic reasons (forstoichiometric coupling, the weight ratio of polymer to curing agentbeing greater than the weight ratio of monomer to curing agent) andbecause polymers are generally more often used in elastomericapplications than are monomers. The molecular weight of the polymers tobe cured can be selected over a wide range, generally lying within therange from about 100 to about 100,000. However, generally the polymerspreferred in the practice of the invention will have a molecular weightgreater than about 1,000; and often the polymers will have a molecularweight greater than about 10,000 and less than about 20,000. Suitablepolymers include polymers which are liquid (i.e., pourable) at aboutroom temperature as well as polymers which are solid at about roomtemperature, although liquid polymers are preferred materials because ofthe ease with which they can be mixed with the curing system. If a solidpolymer is used, it should preferably be ground into small pieces anddissolved in a liquid, which liquid should preferably be one of theliquid components of the composition which is to be prepared.

Although, as discussed above, any mercaptan-containing compound can beused in the practice of the invention, it is preferred that at least twoand more preferably 3 to 5 mercaptan groups per molecule on the averagebe present. The average number of mercaptan groups per molecule of amaterial is the average mercaptan functionality of that material. Whentwo or more such groups are present, upon curing, the cured compositionacquires substantial elastomeric character. If only one mercaptan groupis present on a molecule, elastomeric character would generally not beacquired to a substantial extent upon curing.

In the following examples, a mercaptan-containing liquid PM Polymer* wasused. This material is mostly apoly(oxyalkylene)-polyester-poly(monosulfide)-polythiol, the propertiesof which are described below. Methods of preparation of this polymer arewell known in the art, for example in U.S. Pat. No. 3,817,936 and in therecently allowed application having Ser. No. 737,948.

Two methods for preparing thepoly(oxyalkylene)-polyester-poly(monosulfide)-polythiols which have atleast three mercapto groups, which are known in the art, and which arecured with the curing system of the present invention are: (1) reactingat least one mercapto-alkanoic acid and at least one thiodialkanoic acidwith poly(oxyalkylene)-polyols having at least three pendant hydroxygroups per molecule or (2) reacting a mercapto-alkanoic acid ester and athiodialkanoic acid ester with poly(oxyalkylene)-polyols having at leastthree pendant hydroxyl groups per molecule.

When either the method described in U.S. Pat. No. 3,817,936 or themethod described in the application having Ser. No. 737,948 is used, themercaptan-containing polymers which are prepared appear to beessentially the same except for slight differences in stability and pHand exhibit most of the same physical properties. It is believed thatthe curing system described herein performs equally well with polymersmade by either method. However, the PM Polymer used in the examples inthis specification was prepared by the method described in Ser. No.737,948. Properties of a typical sample ofpoly(oxyalkylene)-polyester-poly(monosulfide)-polythiol produced byeither method noted above are shown in Table I. The properties of anindividual sample may vary; and hence ranges are given in Table I whereappropriate.

                  TABLE I                                                         ______________________________________                                        Typical Properties of Poly(Oxyalkylene)-                                      Polyester-Poly(Monosulfide)-Polythiol (PM Polymer)                            ______________________________________                                        Physical state         liquid                                                 Viscosity, poise, 25° C. (77° F.)                                                      70 ± 20                                             Color                  light yellow                                           Mercaptan sulfur, wt. %                                                                              0.85 ± 0.1                                          Estimated molecular weight                                                                           12,000 to 15,000                                       Estimated average mercaptan                                                   functionality per molecule                                                                           3-5                                                    Specific gravity       1.02 ± 0.01                                         Density, lbs/gal       8.3                                                    pH (of a saturated water extract of                                           PM Polymer)            7.03 ± 1.0                                          ______________________________________                                         *Registered Trademark of Phillips Petroleum Company.                     

In the practice of the invention, a curing system comprising a mixtureof two types of ingredients will generally be used. It has been foundthat when both ingredients are present together, a cure is provided;whereas when either material is used alone, no observable amount of cureis obtained. These two materials will be called type A and type B curingagents, both of these materials being metal complexes.

In the practice of the invention, curing agent type A is selected fromthe group consisting of metal substituted dithiocarbamates. These arerepresented by the formula ##STR1## In this formula, M can be any metalor mixture of metals found in Groups IA, IB, IIA, IIB, IVA, VA or VIA ofthe periodic table; Z can be an amino group (i.e., H₂ N-), adisubstituted amino group (i.e., RR'N-, wherein R and R' can be the sameor a different hydrocarbyl group having from 1 to about 18 carbonatoms), a monosubstituted amino group (HRN-, wherein R is a hydrocarbylgroup having from 1 to about 18 carbon atoms), or a heterocyclic aminogroup (for example, piperidine); and x can be 1, 2, 3, or 4, dependingupon the valence of the metal employed. Some examples of suitable type Acuring agents include the following: sodium monoethyldithiocarbamate,sodium di-n-butyldithiocarbamate, calcium diethyldithiocarbamate,cadmium diethyldithiocarbamate, bismuth dimethyldithiocarbamate, copperdimethyldithiocarbamate, zinc monomethyldithiocarbamate, zincdiethyldithiocarbamate, zinc dibutyldithiocarbamate, zincdibenzyldithiocarbamate, lead dimethyldithiocarbamate, seleniumdiethyldithiocarbamate, tellurium diethyldithiocarbamate, zincethylphenyldithiocarbamate, zinc dithiocarbamate, calciumdithiocarbamate and suitable mixtures thereof.

Preferred type A curing agents are the more commonly founddithiocarbamates, for example, zinc dibutyldithiocarbamate, zincdiethyldithiocarbamate, and bismuth dimethyldithiocarbamate.

The second component of the curing system which is required in thepractice of the invention and which is referred to as curing agent typeB can be any Group VIIB or Group VIII metal compound of an organiccarboxylic acid or any Group VIIB or Group VIII metal compound of abeta-diketone. This would include both cyclic and acylic carboxylicacids, where the term "cyclic" includes both aromatic and nonaromaticcompounds. It is believed that the active species in the type B curingagent is generally the metal; and therefore the anion is of lesserimportance. Preferred metals are manganese, iron, cobalt, and nickel.These are preferred because of their usual availability and/or activity.Suitable examples of anions which can be used in the type B curing agentinclude carboxylates, dicarboxylates, and acetyl acetonates. Anions ofmonocarboxylic acids are preferred in the practice of the inventionbecause these anions exhibit good solubility or compatability with theoverall system.

The preferred metal compounds of carboxylic acids are represented by thegeneral formula ##STR2## wherein M' can be any Group VIIB or Group VIIImetal; R" is a hydrocarbyl group having from 1 to 18 carbon atoms; and ywill generally be 1, 2, or 3, depending upon the valence of the metal M'employed. Anions of monocarboxylic acids include for examplepropionates, butyrates, pentanoates, hexanoates, octanoates,ethylhexanoates, decanoates, dodecanoates, and mixtures thereof.

Examples of suitable dicarboxylates which can be used as the requiredtype B curing agent are oxalates, malonates, succinates, glutarates,adipates, pimelates, suberates, azelates, sebacates, and suitablemixtures thereof.

Suitable metal compounds of beta-diketones which can be used as therequired type B curing agent are represented by the formula ##STR3##wherein M' is any Group VIIB or Group VIII metal; the (R'")'s areindividually selected from the group consisting of hydrocarbyl groupshaving from 1 to about 18 carbon atoms per hydrocarbyl group; and y willgenerally be 1, 2, or 3, depending upon the valence of the metalemployed. Examples of these suitable materials include (but are notlimited to): manganese(II) 2,4-pentanedionate (also calledacetylacetonate; manganese(III) 2,4-heptanedionate; nickel(II)2,4-octanedionate; cobalt(II) 2,4-pentanedionate; and cobalt(III)2,4-pentanedionate and mixtures thereof.

It is expected that the type A and type B curing agents as describedabove can be stored together as a separate curing package for subsequentcuring of the basic polymer (the curing occuring when the total combinedsystem is exposed to environmental conditions as herein described).

In the practice of the invention, the curing system can also contain(besides the type A curing agent material, defined above, and the type Bcuring agent material, defined above) calcium peroxide and/or calciumoxide. The presence of calcium peroxide and/or calcium oxide generallyhelps to increase the rate of curing and enhances performance propertiesof the cured elastomeric product. However, the invention in its broadestaspects is not to be construed as limited to requiring the presence ofcalcium peroxide and/or calcium oxide.

Fillers, plasticizers, pigments, antioxidants and similar additives canbe employed with the base material and the curing system of thisinvention. The selection of these additives is left to those skilled inthe art, it being understood that they should be chosen so that they donot produce undesirable products or results with themercaptan-containing base material or the curing system.

The air-curable compositions according to the invention are useful for avariety of purposes, including sealants. When a sealant is to beformulated from the PM Polymer described in Table I, the followingrecipe will preferably be used.

When other mercaptan-containing materials are to be cured, the relativeamounts of curing agents may be varied from those in Table II, dependinggenerally upon the mercaptan content of the material to be cured. As themercaptan content of the material to be cured increases, an increasedamount of curing agents will generally be needed.

                  TABLE II                                                        ______________________________________                                        General Sealant Formulation                                                   Component          Parts by Weight of Polymer                                 ______________________________________                                        A mercaptan-containing polymer,                                               the properties of which are                                                   described in Table I                                                                             100                                                        Filler(s) and pigments                                                                            50-300                                                    Plasticizer         2-20                                                      Thickener           1-10                                                      Antioxidant        0.1-5                                                      Curing agent type A.sup.(a)                                                   Broad              0.05-10                                                    Preferred          0.5-5                                                      Curing agent type B.sup.(b)                                                   Broad              0.005-1.0                                                  Preferred          0.05-0.5                                                   ______________________________________                                         .sup.(a) Metal substituted dithiocarbamate (parts based on total weight o     the metal substituted dithiocarbamate per 100 parts mercaptancontaining       polymer).                                                                     .sup.(b) Metal compound of an organic acid (parts based on metal content      of curing agent type B per 100 parts mercaptancontaining polymer)        

Although the formulation given in Table II is recommended for a sealantwhich is to be used in the building trade, other formulations may bepreferable for other uses. Such formulations would also be within thescope of this invention. The amount of curing agent used is based on theamount of the particular mercaptan-containing polymer employed, and thisratio should generally remain the same for the same polymer regardlessof the product application.

The method of preparing the compositions according to the inventioninvolves adequate mixing of the required ingredients. Generally, toinsure good mixing, all liquids will be placed first into the mixerbeing used; and then solids will be added to the liquids and willpreferably be followed by a vacuum treatment to remove entrapped airand/or oxygen. Therefore, generally the curing agents will be added tothe mixture last and preferably under a nitrogen cover so as to aid insafeguarding against any possible exposure of the mixture to air and/oroxygen.

EXAMPLES

The following examples serve to illustrate this invention; however, theinvention is not to be construed as limited thereto.

The following recipe was used to prepare a pre-mix which was then usedin Examples I and III (described below). This recipe was slightlymodified to prepare the pre-mix for Example II, the only modificationsbeing that pigments (items 7, 8, and 9) were excluded from theformulation (and therefore the weight percents of the ingredients whichwere present in Example II were slightly different from those in thepre-mix recipe given below).

    ______________________________________                                        Recipe for PM Polymer Pre-mix                                                 Ingredient                 Wt. %                                              ______________________________________                                        1.   Mercaptan-containing liquid polymer.sup.(a)                                                             35.0                                           2.   50% Chlorinated paraffin.sup.(b) (plasticizer)                                                          3.8                                            3.   Calcium carbonate.sup.(c) (filler)                                                                      39.3                                           4.   Titanium Dioxide.sup.(d) (filler)                                                                       18.8                                           5.   A fumed silica.sup.(e) (thickener)                                                                      2.5                                            6.   2,2'-Methylene bis(4-methyl-6-t-butyl phenol).sup.(f)                         (antioxidant)             0.28                                           7.   A cadmium-based pigment.sup.(g)                                                                         0.18                                           8.   Iron oxide.sup.(h) (pigment)                                                                            0.09                                           9.   Carbon black.sup.(i) (pigment)                                                                          0.09                                                Total                     100.04                                         ______________________________________                                         .sup.(a) PM Polymer  Phillips Petroleum Company prepared by the method        described in allowed case having Serial No. 737,948, which method is          described below.                                                              .sup.(b) Clorafin® 50  Hercules Incorporated.                             .sup.(c) Hi Pflex® 100  Pfizer Minerals.                                  .sup.(d) No. 2060  Titanox Pigment Corporation.                               .sup.(e) CabO-Sil®, M5 from the Cabot Corporation.                        .sup.(f) Cyanamid 2246  American Cyanamid.                                    .sup.(g) Yellow Pigment, No. 1476 from Harshaw Chemical.                      .sup.(h) Red pigment, R2199, Pfizer Minerals.                                 .sup.(i) Type N765, Phillips Petroleum Company.                          

Preparation of PM Polymer

The following is a description of a typical preparation of the PMPolymer used in the invention runs in Examples III, IV, and V, describedbelow.

Into a one-gallon stainless steel reactor fitted with a stirrer,pressure gauge, temperature measuring device and internal cooling coilwas placed methanol (600 ml), concentrated ammonium hydroxide (28 weightpercent NH₃, 21.6 gm), sulfur (12 gm) and hydrogen sulfide (816 gm).Methyl acrylate (1376 gm) was introduced into the stirred reactor over a45 minute interval. Over the reaction period the temperature of thereaction mixture increased from 23° C. to 53° C. while the pressuredecreased from 1650 kPa (240 psig) to 1150 kPa (169 psig). After anadditional 30 minute period of stirring the reactor was vented torelease excess hydrogen sulfide and the remaining reaction solution wastransferred to a fractionation apparatus.

A total of 5 runs were made as described above. The resulting reactionmixtures were combined prior to fractional distillation.

A fraction (5889 gm) was collected over a boiling range of 87°-93° C. at50 torr (mm Hg) pressure which contained 98.6 weight percent methyl3-mercaptopropionate (analyzed by GLC, i.e., gas-liquid chromatography).The undistilled pot residue (3005 gm) contained 85 weight percentdimethyl thiodipropionate and 15 weight percent dimethyldithiodipropionate, analyzed by GLC.

Into a 3 liter, stirred, heated glass reactor was added polyether polyol(550 gm of LHT-34 from Union Carbide-derived from 1,2,6-hexanetriol andpropylene oxide, having a molecular weight of about 4500 and a hydroxylnumber, which is the milliequivalents of OH groups per gram of polyol,of about 34). Nitrogen (0.056 m³ /hr) was bubbled through the stirredreactor and the contents maintained at 100° C. for one hour to removeresidual water. The nitrogen flow was then reduced to 0.0056 m³ /hr, areflux condenser was attached and methyl-3-mercaptopropionate (25.9 gmfraction described above), sulfide-disulfide mixture (14.1gm-undistilled pot residue described above), and tetrabutyl titanate(0.2 ml, duPont's Tyzor TBT, essentially 0.2 g pure tetrabutyl titanate)were added to the reactor. The stirred reaction mixture was maintainedat 177° C. for 24 hours. The nitrogen flow through the reaction mixtureswept out the methanol formed in the transesterification reaction. Atthe end of the 24 hour period, the reflux condenser was removed and thenitrogen flow rate was increased to 0.056 m³ /hr with the temperaturemaintained at 177° C. for one hour to remove volatiles. The resultantpoly(oxyalkylene)-polyester-poly(sulfide)-polythiol possessed 0.88weight percent mercaptan sulfur and a viscosity of 6800 centipoises at25° C.

The ingredients given above in the Recipe for PM Polymer Pre-mix weremixed together in a mixer at ambient room temperature generally in theorder listed. The pre-mix was then used in Examples I, II, and III, asdescribed below.

In accordance with ASTM D 638-56T, specimens were formed, were allowedto cure, and were subjected to measurements of several propertiesrelated to the resilience of the specimens. These properties were 50%modulus, tensile strength, and elongation.

Example I (Control)

For purposes of comparison, a two-package sealant composition wasprepared and evaluated. The curing agent was based on lead dioxide.

To 100 grams of the above-described sealant pre-mix was added 2.1 gramsof a curing paste that contained 50 weight percent lead dioxide, 45weight percent dibutyl phthalate and 5 weight percent stearic acid(C-5500, G. P. Roeser Company). The resulting mixture was then cast intoa picture frame mold having dimensions 21/2 inches×21/2 inches×1/8 inch.The composition was allowed to cure at room temperature (about 25° C.)for 14 days. The humidity in the room remained between 45 and 50percent. The surface of the composition became tack-free to polyethylenefilm within 72 hours; but it retained some finger tack even after 2 to 3weeks. Finger tack is tested by touching the specimen being tested withan index finger and noting how tacky (i.e., sticky) the specimen feels.After a period of 14 days, the cured composition was removed from theframe; and some performance properties related to resilience weremeasured by the method of ASTM D 638-56T. Properties measured were asfollows:

    ______________________________________                                        50% modulus:           50 psi                                                 tensile strength:     135 psi                                                 elongation:          >700 percent                                             ______________________________________                                    

Example II (Control)

This example illustrates the unsatisfactory results obtained when oneattempts to cure a particular mercaptan-containing polymer with a curingsystem disclosed in U.S. Pat. No. 3,991,039 comprising a manganese saltof a carboxylic acid and a known sulfur-based rubber cure accelerator(i.e., tetramethylthiuram disulfide). To 50 grams of the sealant pre-mixdescribed above (with the exception that no pigments were present) wasadded 0.1 gram of tetramethylthiuram disulfide (Methyl Tuads) and 0.4gram of a 37.28 weight percent solution of manganese(II)2-ethylhexanoate in mineral spirits (containing 6 weight percentmanganese metal, supplied by Mooney Chemicals under the name 6 percentManganese Hex-Cem® Liquid). After 2.5 weeks at ambient room temperaturein an air atmosphere with a humidity between 45 and 50 percent, themixture had surface cured (i.e., had skinned over) but was still fingertacky. After 11 days at ambient room temperature, a center portion ofthe composition was examined and found to be uncured. This same portionremained uncured for the next 4 days.

Example IIIA (Invention)

To 25 grams of the sealant pre-mix described above was added 0.1 gram ofthe 37.28 weight percent solution of manganese(II) 2-ethylhexanoate inmineral spirits (containing 6 weight percent manganese metal), describedabove, and 0.1 gram zinc dibutyldithiocarbamate. The ingredients werethoroughly mixed for about 1 to 3 minutes, and the mixture was thenimmediately spread into the same type of picture frame mold as describedin Example I. Although the composition was not stored before use,Example IV demonstrates storage ability of the inventive composition.

When the inventive composition was exposed to air, the sealant becamesurface tack-free to polyethylene within the short time period of 45minutes. Although finger tack in this particular run was not tested,finger tack of another example of the inventive composition was testedin Example IIIC, described below. After about 5.5 weeks of exposure toair, the specimens were removed from the mold and the followingproperties were measured:

    ______________________________________                                        50% modulus:          27 psi                                                  tensile strength:    103 psi                                                  elongation:          755 percent                                              ______________________________________                                    

The properties of the inventive composition compare very favorably withthose of the standard two-package sealant prepared and described inExample I. This is significant in that (as described above) atwo-package system will generally give better cured performanceproperties than a one-package sealant system (provided that human errorscan be excluded from the mixing step in the preparation).

Example IIIB (Invention)

A composition similar to that described in Example IIIA was preparedfrom 50 grams of the sealant pre-mix described above, 0.2 gram of the37.28 weight percent solution of manganese(II) 2-ethylhexanoate inmineral spirits (containing 6 weight percent manganese metal) describedabove, 0.2 gram of zinc dibutyldithiocarbamate, and 2 grams of calciumoxide. Surface curing was observed to occur almost immediately, asindicated by "skinning" within 1-2 minutes.

In another invention run, wherein calcium peroxide was employed insteadof calcium oxide, skinning and subsequent internal curing also occurredfaster than when neither calcium peroxide nor calcium oxide was present.

Example IIIC (Invention)

A composition similar to that described in Example IIIA was preparedfrom 25 grams of the sealant pre-mix described above, 0.2 gram of the37.28 weight percent solution of manganese(II) 2-ethylhexanoate inmineral spirits (containing 6 weight percent manganese metal) describedabove, and 0.1 gram of zinc dibutyldithiocarbamate. The ingredients werethoroughly mixed for 1 to 3 minutes, and the mixture was then spreadinto the same type of picture frame mold as described in Example I.After being exposed to air with a relative humidity between 45 and 50percent for 2.5 weeks, the composition was tested for finger tack. Itwas found to be less finger tacky than the composition of Example II(Control), both compositions having been exposed to air for the samelength of time.

                                      TABLE III                                   __________________________________________________________________________    Summary of Data from Examples I, II, IIIA, IIIB, and IIIC                     Example:          I    II    IIIA   IIIB   IIIC                                                 (Control)                                                                          (Control)                                                                           (Invention)                                                                          (Invention)                                                                          (Invention)                        __________________________________________________________________________    I. 35 weight percent                                                             PM Polymer                                                                    pre-mix        100g 50g.sup.(k)                                                                         25g    50g    25g                                II.                                                                              Curing Agents:                                                             a.   50 weight percent                                                             lead dioxide                                                                  paste        2.1g --    --     --     --                                 b.   57 weight percent                                                             calcium peroxide                                                              paste        --   --    --      2g    --                                 c.   Manganese (II)                                                                2-ethylhexanoate.sup.(l)                                                                   --   0.4g  0.1g   0.2g   0.2g                               d.   Zinc di-n-butyldithio-                                                        carbamate.sup.(m)                                                                          --   --    0.1g   0.2g   0.1g                               e.   Tetramethylthiuram                                                            disulfide.sup.(n)                                                                          --   0.1g  --     --     --                                 III.                                                                             Cured Performance Properties:                                              a.   50 percent modulus,                                                           psi           50  --     27    --     --                                 b.   Tensile strength,                                                             psi          135  --    103    --     --                                 c.   Percent elongation                                                                         700  --    755    --     --                                 IV.                                                                              Comments:      Tacky                                                                              Cured in                                                                            Tack free                                                                            Skinning                                                                             Less tacky                                           (finger                                                                            2.5 wks.                                                                            to poly-                                                                             within 1-2                                                                           (finger                                              tacky)                                                                             but more                                                                            ethylene.sup.(o)                                                                     minutes.                                                                             tacky) than                                          after 2                                                                            tacky after 45 min.                                                                        (No fin-                                                                             Ex. II after                                         to 3 wks.                                                                          (finger      ger tack                                                                             2.5 wks.                                                  tacky) than  after 2 min.)                                                    Ex. IIIC                                               __________________________________________________________________________     .sup.(k) Contains 0 weight percent pigments.                                  .sup.(l) 6 weight percent Mn HexCem.                                          .sup.(m) Butyl Zimate. Trademark R. T. Vanderbilt Co., Inc.                   .sup.(n) Methyl Tuads. Trademark R. T. Vanderbilt Co., Inc.                   .sup.(o) Tested as described in Federal Specification TTS-00230C.        

Example IV (Invention)

The following example further illustrates the usefulness of anembodiment of the present invention as a one-package sealant suitablefor use in the building trade. The recipe shown below was used toprepare a formulation which was subjected to Federal Specification TestTT-S-00230C for single package elastomeric building sealants, Type II(non-sag), Class A. The formulation was also subjected to a series ofviscosity measurements.

    ______________________________________                                        Recipe                                                                        Component                Weight Percent                                       ______________________________________                                        Mercaptan-containing PM Polymer                                                                        34.70                                                Calcium carbonate (Hi Pflex 100) (filler)                                                              38.98                                                Titanium Dioxide (filler)                                                                              18.65                                                50% chlorinated paraffin (Clorafin 50)                                        (plasticizer)            3.77                                                 Fumed silica (Cab-O-Sil, M5) (thickener)                                                               2.48                                                 2,2'-Methylene bis(4-methyl-6-t-butyl phenol)                                 (Cyanamid 2246) (antioxidant)                                                                          0.28                                                 Zinc dibutyldithiocarbamate                                                                            0.35                                                 6 percent Mn Hex-Cem Liquid                                                                            0.79                                                                          100.00                                               ______________________________________                                    

Samples were prepared, were allowed to cure, and were subjected to testsin accordance with Federal Specification TT-S-00230C.

It was observed that the samples skinned over immediately upon exposureto air after the one-package composition had been stored inside ahermetically-sealed container for about 24 to about 48 hours.

These samples were subjected to various tests for a one-package sealantcomposition as specified in Federal Specification TT-S-00230C. All ofthese tests examine various performance properties of the sealant. Thetest requirements and results for the inventive sealant specimens aredisplayed in Table IV. A series of viscosity measurements were also runon samples of the inventive sealant composition; and the results areshown in Table V.

                                      TABLE IV                                    __________________________________________________________________________    One-Package PM Polymer-Based Sealant Performance                              According to Federal Specification TT-S-00230C                                Test            Substrate.sup.a                                                                     Required Value                                                                        Value Obtained                                  __________________________________________________________________________      Canvas Peel, ppiw                                                                           Glass >5      25                                                              Aluminum                                                                            >5      35                                                              Concrete                                                                            >5       9                                                Canvas Peel After UV                                                                        Glass >5      Adhesive Failure.sup.b                            and H.sub.2 O Exposure, ppiw                                                  Durability, ± 25% exten-                                                                 Glass 10 cycles                                                                             passed                                            sion-compression at                                                                         Aluminum                                                                            10 cycles                                                                             passed                                            25° C. Concrete                                                                            10 cycles                                                                             failed.sup.b                                      Durability, ± 25% exten-                                                                 Glass 10 cycles                                                                             passed                                            sion-compression between                                                                    Aluminum                                                                            10 cycles                                                                             passed                                            -26° C. (-15F.) and 70° C.                                                    Concrete                                                                            10 cycles                                                                             not tested.sup.c                                  (158° F.)                                                              Hardness, A2 Durometer                                                                      --    ≧15 and ≦50                                                             34                                                at 25° C.                                                              Weight Loss, after heat                                                                     --     ≦10%                                                                          1.1%                                              treatment at 70° C.                                                    Tack-free (to polyethylene                                                                  --    ≦72                                                                            1-2                                               film) time, hours                                                             Stain/Color   Concrete                                                                            no stain                                                                              no stain                                          Extrusion Rate, seconds                                                                     --    ≦45                                                                            9-10                                            10.                                                                             Sag, 4.4° C. (40° F.), inches                                                 --     ≦3/16                                                                         1/16                                              50° C. (122° F.), inches                                                      --     ≦3/16                                                                         1/16                                            __________________________________________________________________________     .sup.a All surfaces were primed with a mixture of 86.8 wt. % P47 primer       and 13.2 wt. % A187. A187 is gammaglycidoxypropyl trimethoxy silane           available from Union Carbide. P47 is a 10 wt. % of an isocyanate dissolve     in toluene.                                                                   .sup.b Failure attributed to improper selection of primer.                    .sup.c Failed in previous test (See test 3, described above).            

The data in Table IV show that the inventive composition prepared inExample IV is quite satisfactory for use as a sealant in the buildingtrade.

For surfaces of aluminum, the sealant passed all of the ten performancetests required for a one-package sealant under Federal SpecificationTT-S-00230C. For surfaces of concrete and glass, the sealant passed mostof those ten tests; and where failure was observed, it is believed thatit was due to the primer used and was not due to the sealant since thefailure was always at the sealant-substrate interface.

As described above, a one-package sealant composition must be able toremain relatively uncured in a container for a reasonable length of timeand must then begin to cure only after exposure to environmentalconditions, for example, air or oxygen. In order to demonstrate thestability of a sample of the inventive composition during an extendedperiod of storage (and thus to demonstrate its usefulness as aone-package sealant system), a series of viscosity measurements onspecimens of the sealant composition were made at 25° C. Samples of thefreshly mixed sealant composition were placed in a number ofscrew-capped no. 9 dram glass vials. These were stored at ambient roomtemperature for various periods of time. Then each vial and its contentswere placed in a constant temperature bath at 25° C. for 1 hour; andafter this time period, the viscosity in centipoises (Cps) and inPascal-seconds (Pa.S) was measured, using a Brookfield Viscometer ModelRVT-E with a No. 7 spindle. Measurements were made at various speedsgiven in revolutions per minute (rpm); and the data are shown in TableV.

                                      TABLE V                                     __________________________________________________________________________    Storage Stability of One-Package                                              PM Polymer-Based Sealant                                                              Viscosity at 25° C. Using Various Spindle Speeds               Time in Storage                                                                       0.5 rpm        1.0 rpm        5 rpm                                   at 25° C., Days                                                                Pa . S × 10.sup.-3                                                              Cps × 10 .sup.-3                                                               Pa . S × 10.sup.-3                                                              Cps × 10.sup.-3                                                                Pa . S × 10.sup.-3                                                              Cps × 10.sup.-3           __________________________________________________________________________    2       3.03    3,030  1.69    1,690  0.591   591                             31      3.28    3,280  1.80    1,800  0.624   624                             57.sup.a                                                                              2.84    2,840  1.72    1,720  0.536   536                             __________________________________________________________________________     .sup.a Extruded sample skins over in 1-2 hours, indicating cure               initiation.                                                              

The data in Table V shows no significant increase in viscosity ofspecimens after they have been stored for as long as 57 days. Therefore,the composition does not appear to cure to a substantial extent while itis hermetically stored. Thus, it is suitable for use as a one-packagesystem.

Example V

In this example, control runs VA and VB demonstrate that no observableamount of cure is obtained when either the type A curing agent or thetype B curing agent was used alone to cure a mercaptan-containingpolymer. Control run VC shows that no cure was effected when both thetype A and type B curing agents were absent from the formulation. Aninvention run VD is included to show that a cure was achieved when bothtype A and type B curing agents were used together. An invention run VEwas included to show the changes in the formulation of run VD made toimprove sag properties.

    __________________________________________________________________________    RECIPE                                                                                      Weight Percent                                                                Run VA                                                                             Run VB                                                                             Run VC                                                                             Run VD                                                                              Run VE                                     Ingredient    (Control)                                                                          (Control)                                                                          (Control)                                                                          (Invention)                                                                         (Invention)                                __________________________________________________________________________      Mercaptan-containing                                                          liquid polymer.sup.(a)                                                                    30   30   30   30    23.5                                         Calcium carbonate.sup.(b)                                                     (filler)    50   50   50   50    60                                           Liquid polyester.sup.(c)                                                      (plasticizer)                                                                             15   15   15   15    11.5                                         Titanium dioxide.sup.(d)                                                      (filler)    1.0  1.0  1.0  1.0   1.0                                          Fumed silica.sup.(e)                                                          (thickener) 1.7  1.7  1.7  1.7   1.7                                          2,2'-Methylene bis(4-                                                         methyl-6-t-butyl                                                              phenol).sup.(f)                                                               (antioxidant)                                                                             0.3  0.3  0.3  0.3   0.3                                          Sorbitan monostearate.sup.(g)                                                 (surface active agent)                                                                    1.0  1.0  1.0  1.0   1.0                                          Surface active agent.sup.(h)                                                              1.0  1.0  1.0  1.0   1.0                                          Manganese II 2-ethyl-                                                         hexanoate.sup.(i)                                                                         0.70 --   --   0.70  0.53                                       10.                                                                             Zinc di-n-butyldithio-                                                        carbamate.sup.(j)                                                                         --   0.35 --   0.35  0.27                                       __________________________________________________________________________     .sup.(a) PM polymer, described previously.                                    .sup.(b) Hi Pflex 100, described previously.                                  .sup.(c) Paraplex G40, obtained from Rohm and Haas Company, average           molecular weight about 6,000, acid no. 1.4 milligrams potassium hydroxide     per gram of sample, saponification no. 585.                                   .sup.(d) No. 2060, obtained from Titanox Pigment Corporation.                 .sup.(e) CabO-Sil, M5, obtained from the Cabot Corporation.                   .sup.(f) Cyanamid 2246, obtained from American Cyanamid.                      .sup.(g) Span 60, obtained from ICI Americas, Inc.                            .sup.(h) Nopco L34A, obtained from Nopco Chemical Company.                    .sup.(i) Six weight percent MnHex Cem, described previously.                  .sup.(j) Butyl Zimate. Trademark R. T. Vanderbilt Co., Inc.              

Formulations were prepared according to the above-described recipe, andthe resulting mixtures were then cast into picture frame molds asdescribed in Example I. The specimens in runs VA, VB, VC, and VD werethen subjected to the same curing conditions. They were all placed in anoven at a temperature of 70° C. for the same length of time (which was aperiod of about 16 to 20 hours).

It was found that in control runs VA and VB, wherein only one of therequired inventive ingredients was used, no observable amount of cureresulted under the curing conditions described above, the samples inthose runs retaining the consistency they had before they were subjectedto the curing conditions. Likewise, in control run VC, no cure resulted.

In invention run VD where both the type A and type B curing agents wereused, under the same curing conditions, a cure was achieved. It is notedthat the formulation in run VD did not have good sag properties, thecured composition having considerable sag (i.e. greater than 3/16 inch).When the relative amount of filler was increased and the relative amountof plasticizer was slightly decreased, as shown in the recipe for runVE, and when that formulation was cured at room temperature (i.e., about25° C.) for 3 weeks, that formulation was found to cure in that timeperiod and to have acceptable sag properties, the sag being less than B3/16 inch. The specimen was then subjected to tests, and the followingproperties were measured:

    ______________________________________                                        50% modulus           33 psi                                                  tensile strength      82 psi                                                  elongation           742 percent                                              ______________________________________                                    

Although the Examples have been described in detail for purposes ofillustrating the invention, the invention is not be construed as limitedthereby. Rather, it is intended to cover reasonable modifications whichwould be apparent to one with ordinary skill in the art.

That which is claimed is:
 1. A method comprising combining at least one type A compound and at least one type B compound,wherein said at least one type A compound is represented by the formula ##STR4## wherein M is selected from the group consisting of metals in groups IA, IB, IIA, IVA, VA, and VIA of the periodic table, wherein x is an integer between 1 and 4, inclusive, and wherein Z is selected from the group consisting of (1) an amino group having the formula H₂ N--, (2) a disubstituted amino group having the formula RR'N--, (3) a monosubstituted amino group having the formula HRN--, and (4) a heterocyclic amino group, wherein R and R' can be the same or different and each comprises a hydrocarbyl group having from 1 to about 18 carbon atoms, and wherein said at least one type B compound is selected from the group consisting of Group VIIB metal compounds of carboxylic acids, Group VIII metal compounds of carboxylic acids, Group VIIB metal compounds of beta diketones, and Group VIII metal compounds of beta diketones.
 2. A method as in claim 1 wherein the at least one type A compound is selected from the group consisting of sodium monoethyldithiocarbamate, sodium di-n-butyldithiocarbamate, calcium diethyldithiocarbamate, cadmium diethyldithiocarbamate, bismuth dimethyldithiocarbamate, copper dimethyldithiocarbamate, zinc monomethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dibenzyldithiocarbamate, lead dimethyldithiocarbamate, selenium diethyldithiocarbamate, tellurium diethyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc dithiocarbamate, and calcium dithiocarbamate.
 3. A method as in claim 1 wherein the at least one type B compound contains at least one cation selected from the group consisting of manganese, iron, cobalt and nickel cations and at least one anion selected from the group consisting of propionate, butyrate, pentanoate, hexanoate, octanoate, ethylhexanoate, decanoate, dodecanoate, oxalate, malonate, succinate, glutarate, adipate, pimelate, suberate, azelate, sebacate, 2,4-pentanedionate, 2,4-heptanedionate and 2,4-octanedionate anions.
 4. A method as in claim 2 wherein the at least one type B compound contains at least one cation selected from the group consisting of manganese, iron, cobalt and nickel cations and at least one anion selected from the group consisting of propionate, butyrate, pentanoate, hexanoate, octanoate, ethylhexanoate, decanoate, dodecanoate, oxalate, malonate, succinate, glutarate, adipate, pimelate, suberate, azelate, sebacate, 2,4-pentanedionate, 2,4-heptanedionate and 2,4-octanedionate anions.
 5. A method as in claim 4 wherein the type A compound is selected from the group consisting of zinc monomethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate and zinc dibenzyldithiocarbamate.
 6. A method as in claim 5 wherein said type A compound is zinc dibutyldithiocarbamate and wherein type B compound is manganese(II)-2-ethyl hexanoate.
 7. A method as in claim 1 wherein from 0.05-10 parts by weight of the at least one type A compound is combined with each 0.005-1.0 parts by weight based on metal content of the at least one type B compound.
 8. A method as in claim 7 wherein from 0.5-5 parts by weight of the at least one type A compound is combined with each 0.05--0.5 parts by weight based on metal content of the at least one type B compound.
 9. A method as in claim 8 wherein the at least one type B compound is selected from the group consisting of compounds represented by the formula ##STR5## wherein M' is selected from the group consisting of Group VIIB and Group VIII metals, wherein R" is hydrocarbyl having from 1 to about 18 carbon atoms and wherein y is 2 or 3, andcompounds represented by the formula: ##STR6## wherein M' is selected from the group consisting of Group VIIB and Group VIII metals, wherein each R'" can be the same or different and is hydrocarbyl having from 1 to about 18 carbon atoms, and wherein y is an integer between 1 and 3, inclusive.
 10. A method comprising combining a mercaptan-containing material with at least one type A compound and at least one type B compound,wherein said at least one type A compound is represented by the formula ##STR7## wherein M is selected from the group consisting of metals in groups IA, IB, IIA, IVA, VA, and VIA of the periodic table, wherein x is an integer between 1 and 4, inclusive, and wherein Z is selected from the group consisting of (1) an amino group having the formula H₂ N--, (2) a disubstituted amino group having the formula RR'N--, (3) a monosubstituted amino group having the formula HRN--, and (4) a heterocyclic amino group, wherein R and R' can be the same or different and each is hydrocarbyl having from 1 to about 18 carbon atoms, and wherein said at least one type B compound is selected from the group consisting of Group VIIB metal compounds of carboxylic acids, Group VIII metal compounds of carboxylic acids, Group VIIB metal compounds of beta diketones, and Group VIII metal compounds of beta diketones.
 11. A method as in claim 10 wherein the mercaptan-containing material is a polymer.
 12. A method as in claim 11 wherein the molecular weight of said polymer lies within the range from about 100 to about 100,000.
 13. A method as in claim 12 wherein the molecular weight of said polymer is greater than about 10,000.
 14. A as in claim 13 wherein said polymer is a liquid at about room temperature.
 15. A method as in claim 14 wherein said liquid mercaptan-containing polymer contains sulfide linkages, the majority of which are mono-sulfide linkages.
 16. A method as in claim 15 wherein said liquid mercaptan-containing polymer is a poly(oxyalkylene)-polyester-poly(monosulfide)-polythiol.
 17. A method as in claim 16 wherein said poly(oxyalkylene)-polyester-poly(monosulfide)-polythiol has a molecular weight within the range from about 12,000 to about 15,000 and an average mercaptan functionality per molecule lying within the range from about 3 to about
 5. 18. A method as in claim 14 wherein the at least one type A compound is selected from the group consisting of sodium monoethyldithiocarbamate, sodium di-n-butyldithiocarbamate, calcium diethyldithiocarbamate, cadmium diethyldithiocarbamate, bismuth dimethyldithiocarbamate, copper dimethyldithiocarbamate, zinc monomethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dibenzyldithiocarbamate, lead dimethyldithiocarbamate, selenium diethyldithiocarbamate, tellurium diethyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc dithiocarbamate, and calcium dithiocarbamate.
 19. A method as in claim 18 wherein said at least one type B compound is selected from the group consisting of compounds represented by the formula: ##STR8## wherein M' is selected from the group consisting of Group VIIB and Group VIII metals,wherein R" is hydrocarbyl having from 1 to about 18 carbon atoms, and wherein y is 2 or 3, and compounds represented by the formula: ##STR9## wherein M' is selected from the group consisting of Group VIIB and Group VIII metals, wherein each R'" can be the same or different and is hydrocarbyl having from 1 to about 18 carbon atoms, and wherein y is an integer between 1 and 3, inclusive.
 20. A method as in claim 19 wherein the at least one type B compound contains at least one cation selected from the group consisting of manganese, iron, cobalt and nickel cations and at least one anion selected from the group consisting of propionate, butyrate, pentanoate, hexanoate, octanoate, ethylhexanoate, decanoate, dodecanoate, oxalate, malonate, succinate, glutarate, adipate, pimelate, suberate, azelate, sebacate, 2,4-pentanedionate, 2,4-heptanedionate and 2,4-octanedionate anions.
 21. A method as in claim 18 wherein the at least one type B compound contains at least one cation selected from the group consisting of manganese, iron, cobalt and nickel cations and at least one anion selected from the group consisting of propionate, butyrate, pentanoate, hexanoate, octanoate, ethylhexanoate, decanoate, dodecanoate, oxalate, malonate, succinate, glutarate, adipate, pimelate, suberate, azelate, sebacate, 2,4-pentanedionate, 2,4-heptanedionate and 2,4-octanedionate anions.
 22. A method as in claim 21 wherein from about 0.05 to about 10 parts by weight of the type A compound and about 0.005 to about 1.0 parts by weight based on metal content of the type B compound are combined with each 100 parts by weight of the mercaptan-containing material.
 23. A method as in claim 22 wherein from about 0.5 to about 5 parts by weight of the type A compound and about 0.05 to about 0.5 parts by weight based on metal content of the type B compound are combined with each 100 parts by weight of the mercaptan-containing material.
 24. A method as in claim 23 further comprising contacting the combined type A compound, type B compound and mercaptan-containing material with oxygen.
 25. A method as in claim 23 further comprising combining a compound selected from the group consisting of calcium oxide and calcium peroxide with the mercaptan-containing material.
 26. A method as in claim 23 further comprising combining with each 100 parts by weight of the mercaptan-containing material, from about 50 to about 300 parts by weight of fillers and pigments, from about 2 to about 20 parts by weight of plasticizer, from about 1 to about 10 parts by weight of thickener, and from about 0.1 to about 5 parts by weight of antioxidant.
 27. A method as in claim 26 further comprising contacting the combined materials with oxygen.
 28. A method comprising contacting a composition comprising a mercaptan-containing polymer combined with at least one type A compound and at least one type B compound with a free oxygen-containing gas,wherein said at least one type A compound represented by the formula ##STR10## wherein M is selected from the group consisting of metals in groups IA, IB, IIA, IVA, VA, and VIA of the periodic table, wherein x is an integer between 1 and 4, inclusive, and wherein Z is selected from the group consisting of (1) an amino group having the formula H₂ N--, (2) a disubstituted amino group having the formula RR'N--, (3) a monosubstituted amino group having the formula HRN--, and (4) a heterocyclic amino group, wherein R and R' can be the same or different and each comprises hydrocarbyl having from 1 to about 18 carbon atoms, and wherein said type B compound is a compound selected from the group consisting of Group VIIB metal compounds of carboxylic acids, Group VIII metal compounds of carboxylic acids, Group VIIB metal compounds of beta diketones, and Group VIII metal compounds of beta diketones.
 29. A method as in claim 28 wherein the free oxygen-containing gas is air.
 30. A method as in claim 29 wherein the composition contains from 0.05-10 parts by weight of the type A compound and from 0.005-1.0 parts by weight based on metal content of the type B compound per each 100 parts by weight of the mercaptan-containing polymer.
 31. A method as in claim 30 wherein the composition contains from 0.5-5 parts by weight of the type A compound and from 0.05-0.5 parts by weight based on metal content of the type B compound for each 100 parts by weight of the mercaptan-containing polymer.
 32. A method as in claim 30 wherein the at least one type A compound is selected from the group consisting of sodium monoethyldithiocarbamate, sodium di-n-butyldithiocarbamate, calcium diethyldithiocarbamate, cadmium diethyldithiocarbamate, bismuth dimethyldithiocarbamate, copper dimethyldithiocarbamate, zinc monomethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dibenzyldithiocarbamate, lead dimethyldithiocarbamate, selenium diethyldithiocarbamate, tellurium diethyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc dithiocarbamate, and calcium dithiocarbamate.
 33. A method as in claim 30 wherein said at least one type B compound is selected from the group consisting of compounds represented by the formula ##STR11## wherein M' is selected from the group consisting of Group VIIB and Group VIII metals, wherein each R" can be the same or different and comprises hydrocarbyl having from 1 to about 18 carbon atoms, and wherein y is 2 or 3, andcompounds represented by the formula ##STR12## wherein M' is selected from the group consisting of Group VIIB and Group VIII metals, wherein each R'" can be the same or different and each comprises hydrocarbyl having from 1 to about 18 carbon atoms, and wherein y is an integer between 1 and 3, inclusive.
 34. A method as in claim 32 wherein the at least one type B compound contains at least one cation selected from the group consisting of manganese, iron, cobalt and nickel cations and at least one anion selected from the group consisting of propionate, butyrate, pentanoate, hexanoate, octanoate, ethylhexanoate, decanoate, dodecanoate, oxalate, malonate, succinate, glutarate, adipate, pimelate, suberate, azelate, sebacate, 2,4-pentanedionate, 2,4-heptanedionate and 2,4-octanedionate anions.
 35. A method as in claim 32 wherein the type B compound contains at least one cation selected from the group consisting of manganese, iron, cobalt and nickel cations and at least one anion selected from the group consisting of propionate, butyrate, pentanoate, hexanoate, octanoate, ethylhexanoate, decanoate, dodecanoate, oxalate, malonate, succinate, glutarate, adipate, pimelate, suberate, azelate, sebacate, 2,4-pentanedionate, 2,4-heptanedionate and 2,4-octanedionate anions.
 36. A method as in claim 35 wherein the molecular weight of said polymer lies within the range of from about 100 to about 100,000.
 37. A method as in claim 36 wherein the molecular weight of said polymer is greater than about 10,000.
 38. A as in claim 37 wherein said polymer is a liquid at about room temperature.
 39. A method as in claim 38 wherein said liquid mercaptan-containing polymer contains sulfide linkages, the majority of which are mono-sulfide linkages.
 40. A method as in claim 39 wherein said liquid mercaptan-containing polymer is a poly(oxyalkylene)-polyester-poly(monosulfide)-polythiol.
 41. A method as in claim 40 wherein the composition further comprises about 50 to about 300 parts by weight of fillers and pigments; about 2 to about 20 parts by weight of plasticizer; about 1 to about 10 parts by weight of thickener; and about 0.1 to about 5 parts by weight of antioxidant per 100 parts by weight of the mercaptan-containing material. 